Diaqua­bis­(nitrato-κO)bis­(pyridine-κN)manganese(II)

The structure of the title manganese complex, [Mn(NO₃)₂(C₅H₅N)₂(H₂O)₂], consists of discrete monomeric entities with Mn²⁺ ions located on centres of inversion. The metal cation is octahedrally coordinated by a trans-N₂O₄ donor set with the pyridine N atoms located in the apical positions. Discrete mol­ecules are linked by O—H...O hydrogen bonds into one-dimensional supra­molecular infinite chains along the b and c axes.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.023
• wR factor = 0.064
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     --  N2      ..        6.0 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A    ..  O2      ..       2.63 Ang.

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  O2      ..        5.5 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  N1      ..        7.3 su
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

In relation to our previous work on the structural chemistry of transition metal complexes (Shahid et al., 2010) as potential precursors for ceramic oxides of the type MO(M = Cu, Zn, Mn, Ni etc), the title compound was prepared as the unintented product of the recation of Mn(NO₃)₂.4H₂O with potassium O-n-butyl xanthate in acetone and pyridine. The asymmetric unit of the title compound contains one pyridine, one nitrate and one water molecule coordinated with one Mn(II) atom. Fig. 1 shows a perspective view of the monomeric unit with the atomic numbering scheme. The Mn(II) atom is in a octahedral environment surrounded by two nitrate, two water and two pyridines ligands. As illustrated in Fig. 1, the Mn(II) atom is six-coordinated observing octahedral geometry with pyridine ligands located at apical positions. The Mn—O distance of nitrate are in good agreement with those reported in similar Mn^II complexes (Saphu et al., 2012). In the crystal structure, molecules are assembled into one dimensional supramolecular infinite chains along bc axis through O—H···O intermolecular hydrogen bonds (Table1, Fig. 2).

Related literature

For our previous work on the structural chemistry of transition metal complexes, see: Shahid et al. (2010). For details concerning the geometric parameters of Mn^II complexes, see: Saphu et al. (2012).

S2. Experimental

Mn(NO₃)₂.4H₂O (0.47 g, 0.27 mmol) was added to a stirred solution of potassium O-n-butyl xanthate(1.0 g,0.53 mmol) in acetone (30 ml). The contents were stirred until complete dissolution of the salt to which about 30 ml of pyridine was added and stirred for 1hr. Filtrate was kept under slow evaporation at room temperature to give the title compound as colourless crystals. Yield 60% (0.42 g), m.p. 373 K. Elemental analysis: calculated (found): C 32.18(31.78), H 3.78(3.35), N 15.01(15.35)%.

S3. Refinement

Water hydrogen atoms were tentatively found in the difference density Fourier map and were refined with an isotropic displacement parameter 1.5 that of the adjacent oxygen atom. The O—H distances were restrained to be 0.84Å within a standard deviation of 0.02 with U_iso(H) =1.5 U_eq(O). All other Hydrogen atoms were placed in calculated positions with C—H distances of 0.95Å for aromatic H atoms with U_iso(H) =1.2 U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2002); data reduction: SAINT-Plus (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. View of the molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level with atom labeling.
	Fig. 2. Packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines.

Diaquabis(nitrato-κO)bis(pyridine-κN)manganese(II)

Crystal data

[Mn(NO3)2(C5H5N)2(H2O)2]	F(000) = 382
Mr = 373.19	Dx = 1.620 Mg m^−3
Monoclinic, P21/c	Melting point: 373 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.8988 (7) Å	Cell parameters from 6452 reflections
b = 11.8668 (10) Å	θ = 2.4–30.5°
c = 7.5950 (6) Å	µ = 0.91 mm^−1
β = 107.500 (1)°	T = 100 K
V = 764.91 (11) Å^3	Block, colourless
Z = 2	0.43 × 0.39 × 0.39 mm

Data collection

Bruker SMART APEX CCD diffractometer	1897 independent reflections
Radiation source: fine-focus sealed tube	1817 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	h = −11→11
Tmin = 0.583, Tmax = 0.701	k = −13→15
6644 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.2526P] where P = (Fo^2 + 2Fc^2)/3
1897 reflections	(Δ/σ)max < 0.001
112 parameters	Δρmax = 0.34 e Å^−3
2 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.73516 (12)	0.28979 (9)	0.04145 (16)	0.0191 (2)
H1	0.6397	0.2500	−0.0121	0.023*
C2	0.87624 (13)	0.23034 (10)	0.08651 (17)	0.0225 (2)
H2	0.8768	0.1517	0.0636	0.027*
C3	1.01597 (13)	0.28769 (10)	0.16539 (17)	0.0217 (2)
H3	1.1140	0.2491	0.1975	0.026*
C4	1.01000 (13)	0.40250 (10)	0.19649 (16)	0.0209 (2)
H4	1.1038	0.4440	0.2507	0.025*
C5	0.86473 (13)	0.45545 (9)	0.14696 (15)	0.0185 (2)
H5	0.8614	0.5342	0.1681	0.022*
Mn1	0.5000	0.5000	0.0000	0.01221 (8)
N1	0.72797 (10)	0.40102 (8)	0.07038 (12)	0.01619 (18)
N2	0.62538 (9)	0.58526 (7)	0.40827 (11)	0.01339 (17)
O1	0.38723 (9)	0.37524 (6)	0.12260 (10)	0.01650 (16)
H1A	0.3806 (18)	0.3081 (12)	0.085 (2)	0.025*
H1B	0.3892 (18)	0.3773 (14)	0.2317 (19)	0.025*
O2	0.58830 (9)	0.61467 (7)	0.23972 (10)	0.01857 (17)
O3	0.64860 (10)	0.48619 (6)	0.45430 (12)	0.01931 (17)
O4	0.63944 (9)	0.66239 (6)	0.52668 (10)	0.01668 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0167 (5)	0.0158 (5)	0.0234 (5)	−0.0013 (4)	0.0042 (4)	−0.0019 (4)
C2	0.0206 (5)	0.0153 (5)	0.0303 (6)	0.0011 (4)	0.0057 (4)	−0.0027 (4)
C3	0.0162 (5)	0.0206 (5)	0.0273 (6)	0.0029 (4)	0.0051 (4)	0.0010 (4)
C4	0.0161 (5)	0.0202 (5)	0.0242 (5)	−0.0024 (4)	0.0026 (4)	−0.0007 (4)
C5	0.0187 (5)	0.0141 (5)	0.0212 (5)	−0.0015 (4)	0.0039 (4)	−0.0013 (4)
Mn1	0.01386 (13)	0.01072 (13)	0.01179 (12)	−0.00029 (7)	0.00348 (9)	−0.00047 (7)
N1	0.0160 (4)	0.0152 (4)	0.0171 (4)	−0.0005 (3)	0.0046 (3)	−0.0003 (3)
N2	0.0134 (4)	0.0130 (4)	0.0136 (4)	−0.0001 (3)	0.0037 (3)	−0.0008 (3)
O1	0.0238 (4)	0.0131 (4)	0.0138 (3)	−0.0021 (3)	0.0075 (3)	−0.0013 (3)
O2	0.0277 (4)	0.0160 (4)	0.0107 (3)	−0.0003 (3)	0.0038 (3)	0.0001 (3)
O3	0.0250 (4)	0.0122 (4)	0.0199 (4)	0.0026 (3)	0.0055 (3)	0.0022 (3)
O4	0.0240 (4)	0.0134 (4)	0.0122 (3)	−0.0010 (3)	0.0049 (3)	−0.0025 (3)

Geometric parameters (Å, º)

C1—N1	1.3428 (14)	Mn1—O1	2.1513 (8)
C1—C2	1.3902 (15)	Mn1—O1^i	2.1514 (8)
C1—H1	0.9500	Mn1—O2^i	2.2189 (7)
C2—C3	1.3856 (16)	Mn1—O2	2.2189 (7)
C2—H2	0.9500	Mn1—N1^i	2.2646 (9)
C3—C4	1.3864 (16)	Mn1—N1	2.2646 (9)
C3—H3	0.9500	N2—O3	1.2262 (11)
C4—C5	1.3839 (15)	N2—O4	1.2627 (11)
C4—H4	0.9500	N2—O2	1.2710 (11)
C5—N1	1.3457 (13)	O1—H1A	0.843 (13)
C5—H5	0.9500	O1—H1B	0.824 (13)
N1—C1—C2	122.85 (10)	O2^i—Mn1—O2	180.00 (3)
N1—C1—H1	118.6	O1—Mn1—N1^i	87.58 (3)
C2—C1—H1	118.6	O1^i—Mn1—N1^i	92.42 (3)
C3—C2—C1	118.93 (10)	O2^i—Mn1—N1^i	93.06 (3)
C3—C2—H2	120.5	O2—Mn1—N1^i	86.94 (3)
C1—C2—H2	120.5	O1—Mn1—N1	92.42 (3)
C2—C3—C4	118.74 (10)	O1^i—Mn1—N1	87.58 (3)
C2—C3—H3	120.6	O2^i—Mn1—N1	86.94 (3)
C4—C3—H3	120.6	O2—Mn1—N1	93.06 (3)
C5—C4—C3	118.71 (10)	N1^i—Mn1—N1	180.0
C5—C4—H4	120.6	C1—N1—C5	117.46 (9)
C3—C4—H4	120.6	C1—N1—Mn1	123.68 (7)
N1—C5—C4	123.30 (10)	C5—N1—Mn1	118.85 (7)
N1—C5—H5	118.3	O3—N2—O4	121.32 (9)
C4—C5—H5	118.3	O3—N2—O2	121.39 (9)
O1—Mn1—O1^i	180.0	O4—N2—O2	117.29 (8)
O1—Mn1—O2^i	80.61 (3)	Mn1—O1—H1A	119.7 (11)
O1^i—Mn1—O2^i	99.39 (3)	Mn1—O1—H1B	122.9 (11)
O1—Mn1—O2	99.39 (3)	H1A—O1—H1B	110.5 (15)
O1^i—Mn1—O2	80.61 (3)	N2—O2—Mn1	125.36 (6)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O4^ii	0.82 (1)	1.98 (1)	2.7805 (11)	163 (2)
O1—H1A···O2^iii	0.84 (1)	2.63 (2)	3.2504 (11)	132 (1)
O1—H1A···O4^iii	0.84 (1)	1.91 (1)	2.7495 (11)	174 (2)

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+1/2.